EP0542964B1 - Alkyles cyclopentenes a substitution hydroxy ou oxo - Google Patents

Alkyles cyclopentenes a substitution hydroxy ou oxo Download PDF

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Publication number
EP0542964B1
EP0542964B1 EP92911560A EP92911560A EP0542964B1 EP 0542964 B1 EP0542964 B1 EP 0542964B1 EP 92911560 A EP92911560 A EP 92911560A EP 92911560 A EP92911560 A EP 92911560A EP 0542964 B1 EP0542964 B1 EP 0542964B1
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EP
European Patent Office
Prior art keywords
trimethyl
cyclopenten
dimethyl
pentan
sandalwood
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP92911560A
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German (de)
English (en)
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EP0542964A1 (fr
Inventor
Bernard Auger
Edouard Giraudi
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Givaudan SA
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Givaudan Roure International SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/21—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/05—Alcohols containing rings other than six-membered aromatic rings
    • C07C33/12—Alcohols containing rings other than six-membered aromatic rings containing five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/516—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of nitrogen-containing compounds to >C = O groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/225—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing rings other than six-membered aromatic rings

Definitions

  • the present invention relates to the field of perfumery. It concerns in particular a hydroxylated compound derived from ⁇ -campholene aldehyde, namely of the formula or 3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-pentan-2-ol, and its use as a fragrance.
  • sandalwood note is highly sought after in perfumery. It is found in the natural essence of sandalwood, which is highly rated by the perfumer, not only because of its odorant character, but also owing to the fixative properties which it imparts in a number of compositions of various types.
  • the main compound which is responsible for the sandalwood odour in this essential oil is (-)- ⁇ -santalol, but two other components, (+)- ⁇ -santalol and lanceal, also contribute to the odour.
  • R.E. Naipawer (US-PS 4,052,341) has established that the compounds of the formula have a strong sandalwood odour.
  • Such a molecule can be prepared efficiently by using as starting material ⁇ -campholene aldehyde, which is obtained by extensively described methods by re-arrangement of epoxypinane (L.C. King and H. Farber, J. Org. Chem. 26 , 326 (1961)).
  • the enantiomerically pure forms of this compound can be obtained by using either (-)- ⁇ -epoxypinane or (+)- ⁇ -epoxypinane as starting compound (Beilstein E III 7 page 355) and can be used individually or as a mixture.
  • Suitable reducing agents are the usual reducing agents and methods respectively for ketones, i.e. complex hydrides, such as alkalimetal borohydrides and LiHH4, Red-Al, or also the Meerwein-Panndoyl reagents, etc.
  • Compound I' is the only one to have the woody, chalky, hard edge of the natural sandalwood essence while sandalore is predominant in the sweet, milky tonality.
  • Polysantol has something of the woody edge of compound I' and also something of the milky edge of sandalore, but with tones which are floral and strange due to its "complex perfumery" edge to the natural sandalwood note.
  • Compound I' therefore offers pronounced advantages for use in the field of perfumery.
  • this product whose odour is pronounced of the natural sandalwood odour, allows many harmonies with the whole range of natural and synthetic products which are universally known in perfumery and also with the head, middle and base components.
  • sandalwood bases contained each - instead of I' - an equal amount of sandalwood essence, or Bacdanol (A), or Sandalore (B), or Polysantol (C) Sandal wood oil.
  • the use percentage of compound I' can vary within a very wide range, from 0.1% in mass-market household products up to 25% in alcoholic extracts for designer perfumery, but these percentages are not limiting since the olfactory principle of this novel product allows great flexibility in use. Such values must not be interpreted in a restrictive manner since they depend on the nature of the product to be perfumed, on the nature of the other compounds which are present in the composition, and on the desired effect.
  • 3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)pentan-2-ol can be incorporated in various use percentages into a large range of composition for any type of application used in the field of perfumery. With its olfactory note, it provides the necessary complement to the woody, dry tone of natural sandalwood.
  • Example 7 its use in a composition for a deodorant is illustrated,
  • Example 8 relates to a composition for a fabric softener, and
  • Example 9 to a composition for a designer perfume.
  • Examples 1 to 9 which are described below are intended to illustrate in a nonlimiting manner the possible preparations and applications of the compound I' in the field of perfumery.
  • a 3-litre three-necked flask equipped with a mechanical stirrer, a condenser, a dropping funnel, a thermometer pocket and a nitrogen supply is charged with 53.2 g of NaBH4 (1.4 mol) and 520 ml of absolute EtOH.
  • the mixture is cooled to 0°C ⁇ t ⁇ 5°C and, in the course of 2 hours, 152 g of ⁇ -campholene aldehyde are added (1 mol, GC purity 85%).
  • the mixture is stirred for another 2 hours at 0°C ⁇ t ⁇ 5°C, and then allowed to return to room temperature.
  • the mixture is covered with 1600 ml of water. Countercurrent extraction is carried out with 2 300 ml of ethyl ether.
  • a 250-ml three-necked apparatus equipped with a mechanical stirrer, a reflux condenser, a dropping funnel and a thermometer pocket is placed under a nitrogen atmosphere is charged with 2.4 g of magnesium (0.1 at/g), and a mixture of 10.9 g of ethyl bromide (0.1 mol) in 12 ml of dry tetrahydrofuran is added. 15.3 g of isobutylenecyclohexylamine (0.1 mol), previously prepared by the method of R. Tiollais, Bull. Soc. Chim. France, 1947, page 715 and dissolved in 16 ml of dry THF are subsequently added to the tetrahydrofuran reflux.
  • the mixture is cooled to room temperature, and 21 g of 2-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-1-bromoethane (0.1 mol) in 25 ml of dry THF are added over 15 minutes.
  • the mixture is refluxed for 12 hours, hydrolysed (carefully) with 80 ml of 10% strength HCl, and stirred for another 3 hours while refluxing the THF.
  • a 50-ml flask equipped with a magnetic stirrer, a reflux condenser, a dropping funnel and a thermometer pocket is placed under a nitrogen atmosphere and charged with 0.53 g of magnesium (0.022 at/g), and a mixture of 3 g of methyl iodide (0.021 mol) in 6 ml of anhydrous ethyl ether is added.
  • the reaction is exothermal, and reflux conditions are maintained for 30 minutes after the end of the addition.
  • the mixture is cooled to 0°C, and a solution of 4 g of 2,2-dimethyl-4-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)butan-1-al (0.019 mol) in 6 ml of anhydrous ethyl ether is run in at this temperature. Stirring is continued for 30 minutes at 0°C after the end of the addition, the mixture is allowed to return to room temperature, and stirring is continued for one hour at this temperature. The mixture is cooled to 0°C, and 20 ml of aqueous 10% strength ammonium chloride solution are run in. The mixture is transferred to a separating funnel, separated and extracted three times with 30 ml portions of ethyl ether.
  • a 500-ml three-necked apparatus equipped with a central mechanical stirrer, a reflux condenser and a thermometer pocket is placed under a nitrogen atmosphere and charged with 76 ml of anhydrous dimethylformamide, 18 g of 2-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-1-bromoethane (0.08 mol) and 6.4 g of 3-methyl-2-butanone (0.075 mol).
  • the mixture is cooled to 0°C and 7.16 g of 50% sodium hydride in Bayol (0.149 mol) [a paraffine oil] are added.
  • a 250-ml three-necked apparatus equipped with a central mechanical stirrer, a reflux condenser, a thermometer pocket and a dropping funnel is placed under a nitrogen atmosphere and charged with 50 ml of anhydrous ethyl ether and 2 g of lithium aluminium hydride (0.052 mol).
  • the mixture is cooled, and a solution of 6 g of 3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-pentan-2-one (0.027 mol) in 50 mol of anhydrous ethyl ether is run in dropwise with stirring.
  • the addition has ended, the mixture is allowed to return to room temperature, and stirring is continued for 3 hours.
  • the mixture is cooled to -5°C, and 2 ml of water and then 2 ml of 15% strength aqueous sodium bicarbonate solution and 6 ml of water are added.
  • the mixture is filtered on a glass sinter, the filter cake is washed with ethyl ether, and the filtrate is concentrated on a Rotavapor apparatus.
  • the crude reaction product is purified by a flash pass through a silica column (eluant 5/95 Et2O/PE).
  • 3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)pentan-2-ol imparts a great deal of sophistication to this composition and heightens the freshness character while giving it greater volume and persistence, by combining with this impression of sea-spray freshness, a certain warm bottom note.
  • This new substance has an effect both on the top and bottom notes of this composition by developing its very natural edge.
  • volume, richness and warmth are imparted to this floral, fruity, green, woody harmony with a classical cypress note in which the excess of the sandalwood note due to the 3,3-dimethyl-5-(2',2'-3'-trimethyl-3'-cyclopenten-1'-yl)pentan-2-ol directs the warm tone towards a floral oriental harmony.
  • the harmony imparted by the 3,3-dimethyl-5-(2',2'-3'-trimethyl-3'-cyclopenten-1'-yl)pentan-2-ol also works well with the floral peel of the top note and the sweet woody bottom note.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention se rapporte au domaine de la parfumerie. Elle concerne notamment un composé hydroxylé dérivé de α-campholène aldéhyde, correspondant à la formule (I), ou 3,3-diméthyle-5-(2',2',3'-triméthyl-3'-cyclopentène-1'-yl)-pentane-2-ol, et est utilisé comme parfum.

Claims (7)

  1. Procédé pour la préparation du 3,3-diméthyl-5-(2',2',3'-triméthyl-3'-cyclopenten-1'-yl)-pentan-2-ol, caractérisé en ce que l'on réduit un composé de formule
    Figure imgb0016
     dans laquelle R¹ représente un atome d'hydrogène ou le groupe méthyle, la réduction étant réalisée avec un composé organométallique lorsque R¹ représente un atome d'hydrogène.
  2. Compositions odorantes, caractérisées en ce qu'elles contiennent le 3,3-diméthyl-5-(2',2',3'-triméthyl-3'-cyclopenten-1'-yl)-pentan-2-ol.
  3. Utilisation du 3,3-diméthyl-5-(2',2',3'-triméthyl-3'-cyclopenten-1'-yl)-pentan-2-ol, à titre d'agent parfumant.
EP92911560A 1991-06-10 1992-06-04 Alkyles cyclopentenes a substitution hydroxy ou oxo Expired - Lifetime EP0542964B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP91109493 1991-06-10
EP91109493 1991-06-10
PCT/EP1992/001243 WO1992022518A1 (fr) 1991-06-10 1992-06-04 Alkyles cyclopentenes a substitution hydroxy ou oxo

Publications (2)

Publication Number Publication Date
EP0542964A1 EP0542964A1 (fr) 1993-05-26
EP0542964B1 true EP0542964B1 (fr) 1995-09-13

Family

ID=8206808

Family Applications (1)

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EP92911560A Expired - Lifetime EP0542964B1 (fr) 1991-06-10 1992-06-04 Alkyles cyclopentenes a substitution hydroxy ou oxo

Country Status (5)

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EP (1) EP0542964B1 (fr)
JP (1) JPH06500569A (fr)
CA (1) CA2089146A1 (fr)
DE (1) DE69204801D1 (fr)
WO (1) WO1992022518A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69708368T2 (de) * 1996-04-09 2002-09-26 Givaudan S.A., Vernier-Geneve Cyclopentanbutanolderivate als Duftstoffe
EP0801049B1 (fr) * 1996-04-09 2001-11-21 Givaudan SA Dérivés de cyclopentanebutanol comme matières odorantes
JP4503109B2 (ja) 1999-02-09 2010-07-14 ダイセル化学工業株式会社 重合性脂環式化合物
JP2002255774A (ja) * 2001-03-02 2002-09-11 Kao Corp デオドラント剤
GB0506263D0 (en) * 2005-03-29 2005-05-04 Givaudan Sa Skin lightening methods, composition and products
GB0802556D0 (en) * 2008-02-12 2008-03-19 Givaudan Sa Organic compounds

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4149020A (en) * 1978-04-05 1979-04-10 International Flavors & Fragrances Inc. Intermediate for preparation of 2,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-pentanol
DE3562901D1 (en) * 1984-03-23 1988-06-30 Firmenich & Cie Hydroxylated derivatives of campholenic aldehyde, their use as flavouring agents and flavouring compositions containing them
DE3441902C1 (de) * 1984-11-16 1986-01-30 Dragoco Gerberding & Co Gmbh, 3450 Holzminden 4-(2,2,3-Trimethylcyclopent-3-en-1-yl)-but-3-en-1-ole,Verfahren zu deren Herstellung und Verwendung als Riechstoffe

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CA2089146A1 (fr) 1992-12-11
JPH06500569A (ja) 1994-01-20
DE69204801D1 (en) 1995-10-19
EP0542964A1 (fr) 1993-05-26
WO1992022518A1 (fr) 1992-12-23

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